The oil, gas and petrochemical industry desires to efficiently obtain hydrocarbons and process the hydrocarbons to produce desired products. Refining processes involve upgrading, converting or separating hydrocarbons (e.g., crude oil) into different streams, such as gases, light naphtha, heavy naphtha, kerosene, diesel, atmospheric gas oil, asphalt, petroleum coke and heavy hydrocarbons or fuel oil. Similarly, natural gas may be converted into industrial fuel gas, liquefied natural gas (LNG), ethane, propane, liquefied petroleum gas (LPG), and natural gas liquids (NGLs). The oil and gas processes are also often integrated with petrochemical systems to convert refinery streams into chemical products, such as ethylene, propylene or polyolefins.
To convert hydrocarbon feeds into petrochemical or basic chemicals, chemical conversion processes may be utilized. These processes typically involve using thermal or catalytic reactors or furnaces to produce reactive hydrocarbon products, such as acetylene, ethylene or propylene in different proportions. As an example, steam cracking reactors are commonly utilized to convert the hydrocarbon feed into ethylene and acetylene, which may be further processed into various chemical products. The steam cracking reactors are utilized because they provide feed flexibility by being able to utilize gas (e.g., ethane) and liquid (e.g., naphtha through gas oils) feeds.
Historically, the oil and gas refineries utilize the higher value distillates from the hydrocarbon feed, which are typically fungible fuels, such as mogas, natural gas and diesel. As a result, the petrochemical refineries utilize the remaining fractions, such as ethane, propane, naphtha and virgin gas oil, in their processes. However, few chemical conversion processes are able to directly employ natural gas or the lower value refinery feeds, such as aromatic gas oils or fuel oils. As such, there is a need for a process that can produce ethylene and acetylene from different feeds, such as advantaged feeds (e.g., aromatic fuel oils) and/or feeds having lower hydrogen content, for example.
To process these feeds, high-severity operating conditions (e.g., more severe operating conditions, such as higher temperatures) are generally used to produce products having a higher value than the feed. High-severity operating conditions enable methane cracking and aromatic ring cracking, which do not occur at appreciable rates at typical low-severity conditions (e.g., conventional steam cracking conditions). At high-severity operating conditions, the primary products of thermal chemical conversion processes are acetylene and ethylene along with hydrogen (H2) and coke, which may vary in proportion depending on the temperatures, pressures, residence times and feed type utilized in the conversion process. Although high-severity operating conditions typically yield predominately acetylene, acetylene may be further converted to ethylene and ultimately polyethylene or other derivatives using conventional technology. High-severity and low-severity conversion processes are typically based on different pyrolysis reactors, which may include pyrolysis alone or integrated with combustion chemistry. That is, the reactors may include pyrolysis chemistry (e.g., thermochemical decomposition of feed at elevated temperatures in the absence of oxygen) alone or in combination with combustion chemistry (i.e., exothermic chemical reactions between a feed and an oxidant). These pyrolysis reactors can be divided into different types: partial combustion that burns part of the pyrolysis feed, indirect combustion that involves contacting the pyrolysis feed with combustion products, arc process that generate the electric arc or plasma to crack the pyrolysis feed, and thermal pyrolysis. Each of these pyrolysis types differs in the means of generating and transferring the heat for the pyrolysis, but may be broadly characterized as low-severity or high-severity.
Thermal pyrolysis reactors involve heating a solid material (e.g., by combustion) and using the heated solid material to crack the pyrolysis feed. In the thermal pyrolysis processes, the combustion products are typically maintained separate from the reactor effluent. This pyrolysis technique involves different reactors, such as a furnace (e.g., as used in steam cracking), a regenerative reactor (e.g., as used in the Wulff process) and others. For instance, thermal pyrolysis is generally described in various references, such as U.S. Pat. Nos. 7,138,047 and 7,119,240. U.S. Pat. No. 7,119,240 describes an exemplary process for the conversion of natural gas into ethylene. In this process, natural gas is cracked in a furnace, actively quenched, and processed in a reactor to produce ethylene. As another example, U.S. Pat. No. 7,138,047 describes a steam cracking process that mixes a hydrocarbon feed with a dilution steam, flashing the mixture, and vaporizing a portion of the mixture in a pyrolysis reactor. In the process, the pyrolysis feed is passed through tubes in the radiant section of a thermal pyrolysis reactor to crack the pyrolysis feed without contaminating it with combustion products. However, due to the nature of a tubular (metal) furnace, steam cracking is limited to effective cracking temperatures of below 1000° C. and residence times of greater than or equal to (≧) 100 milliseconds (ms), which do not effectively convert either methane or aromatics, thereby limiting the feedstock selection. In addition, energy or furnace heat not used in cracking is partially lost in the furnace flue gas or in the quench, as products are quickly cooled to stop undesired reactions.
The “Wulff” reactor, as described in the IHS, SRI Consulting's Process Economics Program “Acetylene” Report Number 16 (1966) and 16A (1982) along with U.S. Pat. Nos. 2,319,679; 2,678,339; 2,692,819; 3,024,094; 3,093,697 and 3,839,484, uses a reverse-flow pyrolysis reactor, which is operated at temperatures of less than (<) 1400° C., to produce olefins and alkynes, such as acetylene. The pyrolysis feed is heated by refractories which have previously been heated by combustion reactions. The pyrolysis feed is cracked, and then further cooled outside of the reactor. The relatively slow quenching is a characteristic of the Wulff process that leads to coke and soot formation from using inefficient indirect heat transfer (e.g., from checker brick). Coke formation in the reactor provides fuel during the combustion cycle and excess coke or soot may be alleviated by using a light feed, i.e., a hydrocarbon containing a high proportion of hydrogen. However, because the indirect heat transfer limits the rate of heat input in the Wulff process, certain pyrolysis feeds, such as methane, may not be economically processed, which limits the feed flexibility for this process.
Further, while pyrolysis regenerative reactors have been used commercially, these reactors are not widely used for the conversion of certain feeds (e.g., natural gas or fuel oils) into acetylene or ethylene. That is, the inefficient refractories limit heat transfer (both for adding heat necessary for pyrolysis and for removing heat necessary for quenching). As a result, the Wulff reactors typically involve cracking temperatures below 1400° C. and involve the use of more expensive feeds, such as ethane, propane and naphtha. In addition, the poor heat transfer limits lead to greater soot generation resulting in poorer selectivity to desired products.
U.S. patent application Ser. No. 12/814,178 describes a process for preparing a resid-containing hydrocarbon feedstock for use in a regenerative pyrolysis reactor. The reference describes feeding a resid-containing hydrocarbon feedstock to and thermally converting in a visbreaker or coker of a resid having a boiling point of at least 565° C. to form a vapor phase containing cracked hydrocarbons. The converted feed is separated to a vapor phase from remaining non-volatiles and the separated vapor phase is cracked in a regenerative pyrolysis reactor. Visbreakers and cokers, however, are limited in the 565° C. conversion and yield either low value visbreaker tar or coke as a byproduct. Higher conversions are impractical due to increased fouling during thermal conversion.
Moreover, various references describe that the reverse flow reactor is not feasible for converting methane to ethylene. In a comparison of the known acetylene conversion technologies, including the partial combustion, indirect combustion, arc processes, and thermal pyrolysis, the regenerative reactors are considered infeasible for methane to ethylene conversion due to the lower attainable temperatures in the Wulff process. That is, the Wulff process, which has checker bricks or refractory tiles within the reactor, is unable to withstand the constant temperature changes inherent in the process. Further, certain of the references describes that partial oxidation of natural gas to acetylene with heat recovery is the most economical process. These references dismiss the use or lighter feeds, such as methane, because it can not be used economically. As such, the use of a reverse flow reactor is not taught as being possible for various reasons.
Although pyrolysis reactors may be used to convert hydrocarbons into useful products, such as acetylene and ethylene, improved reactions are desired which can make use of a broader range of feeds, such as lower hydrogen content feeds. The use of hydrotreating units to upgrade feed for use in a low-severity pyrolysis reactor has been performed. For example, U.S. Pat. Nos. 3,839,484 and 6,210,561 and U.S. Patent App. Pub. Nos. 2007/0090020; 2007/0090019; and 2007/0090018 are examples of hydrotreating processes that are used to upgrade the feed. However, such hydrotreating units have to substantially convert aromatic hydrocarbons to saturated hydrocarbons for those hydrocarbons to be cracked by the low-severity pyrolysis reactor. The conversion of aromatics to saturates is an expensive process because the cost of hydrogen and the required pressure associated with such equipment. In contrast, hydrotreating merely for molecular weight reduction may be performed at lower pressures, consumes less hydrogen and may be less costly. Accordingly, it is desirable to have a process that may convert high-boiling and low hydrogen content hydrocarbon feeds to high-value petrochemicals, such as ethylene and propylene and their derivatives without the need to saturate aromatic rings. Accordingly, it is desirable to provide a process that converts hydrocarbon feeds having lower hydrogen content into ethylene and/or propylene in an enhanced manner.